Acrylic polymers find widespread application in coatings, paints, and adhesives. They are typically prepared using petroleum-derived monomers. Therefore, incorporation of bio-based resources as a substitute for petroleum-derived materials could make a significant contribution in the development of sustainable products. Bio-based materials that are considered for replacing petroleum-derived monomers are typically derived from soybean and other vegetable oils (fatty acids, triglycerides, and polyols), and from starches and sugars (e.g., lactides and caprolactones). However, these monomers cannot participate in the aqueous polymerization methods that are typically used to prepare acrylate polymers without chemical modification to introduce a reactive double bond that can undergo radical polymerization. To this end, macromonomers from acrylated or hydroperoxidized fatty acids and triglyceride derivatives have been used in mini-emulsion polymerizations to prepare waterborne resin coatings. Similarly, acrylated oleate monomers derived from sunflower oil triglycerides have been copolymerized with methyl methacrylate and 2-ethylhexyl acrylate (EHA), and showed potential as pressure-sensitive adhesives (PSAs).
The ring-opening of L-lactide by 2-hydroxyethyl methacrylate (HEMA) has been used to prepare acrylated poly(lactic acid) (“PLA”) macromonomers for radical copolymerization. For example, Ishimoto et al., Biomacromolecules 2009, 10, (10), 2719-2723 used this method to prepare copolymers of acrylated PLA macromonomers and n-butyl methacrylate (BMA) in a mini-emulsion process. Polyacrylates with 34 wt % biomass contents were achieved, where “biomass content” refers to the percentage of the macromonomer, minus HEMA, incorporated in the polyacrylate polymerization product. However, higher biomass incorporation was not possible.